|Publication number||US5043075 A|
|Application number||US 07/528,578|
|Publication date||Aug 27, 1991|
|Filing date||May 24, 1990|
|Priority date||Jun 8, 1989|
|Also published as||CA2017689A1, DE59002166D1, EP0402347A1, EP0402347B1|
|Publication number||07528578, 528578, US 5043075 A, US 5043075A, US-A-5043075, US5043075 A, US5043075A|
|Inventors||Korger Dietmar, Stephan Astegger, Dieter Eichinger, Heinrich Firgo|
|Original Assignee||Lenzing Aktiengesellschaft|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (9), Non-Patent Citations (2), Referenced by (19), Classifications (13), Legal Events (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The invention relates to a method of removing amines from aqueous solutions thereof, in particular from waste waters obtained in certain cellulose processing methods.
Such amine solutions constitute a problem of waste disposal, because hitherto no method has been known, by which amines can be removed from such waste waters in high yields and in a simple manner. Many amines are known to be toxic and difficult to degrade.
Distillative separation methods are described in the literature. Yet, at amine concentrations of 0.01 to 5% by weight, these methods involve several steps, thus being rather complex and uneconomic.
Even various extraction methods have been tested for removal, having been combined with subsequent distillation. Such a method is known, for instance, from GB-B-1 073 582. However, the amines cannot be removed completely according to this method.
In the journal Khim.Prom-st. (Moscow) 1983 (2), pp. 83 to 85, a method of completely removing morpholine from waste waters is described. According to this method, removal is effected by means of ion exchange. The disadvantage of this method consists in that a plurality of ion exchangers, i.e., two strongly acidic cation exchangers combined with an anion exchanger, must be used and that the morpholine-containing eluates resulting from regeneration are strongly acidic and must be neutralized with adequately large amounts of caustic solution prior to further processing. However, the salts incurred entrain morpholine during crystallization, which, in turn, is disadvantageous in that the salt cannot be waste-disposed directly, but only after further regeneration.
The invention has as its object to eliminate these disadvantages and to provide a simple method of removing amines from aqueous solutions thereof, which is feasible in a cost-saving manner requiring no neutralization step and no energy-consuming separation and regeneration steps.
The method according to the invention is characterized by the combination of the following measures:
contacting the aqueous amine solutions with a cation exchanger whose anchor groups consist of carboxyl groups, in order to charge the cation exchanger with the amines,
treating the charged cation exchanger with an aqueous solution of a weak acid having a pKa larger than 3.0 in order to elute the amines, and
processing the eluate by way of distillation, with a portion of the weak acid being separated from the amines and reclaimed, if desired.
By the ion exchanger used according to the invention, the amines both can be removed practically quantitatively in a single pass and can be re-eluted with weak acids. Among these, volatile acids having boiling points of below 120° C., such as formic acid, acetic acid or carbonic acid, have proved particularly suitable.
An advantageous embodiment of the method according to the invention consists in that the pH of the aqueous solution of the acid ranges between 1.7 and 2.8.
The eluate, which contains the amines, acid and water, is further processed by distillation, the distillate containing the acid, water and merely traces of amines and, thus, being apt for recycling into the process. It may, for instance, be used for rinsing the ion exchanger after regeneration. Moreover, it is possible to prepare a fresh regenerant solution by adding concentrated acid. The amines remain in the distillation residue in the form of ammonium salts, e.g., as formates and acetates, together with acid residues. The amines present in a concentrated form can be further processed according to various methods described in the literature or, preferably, can be disposed by being burnt completely.
The invention will be explained in more detail by way of the following examples.
50 ml LEWATIT CNP 80 (a cation exchanger whose anchor groups consist of carboxyl groups) (manufacturer: Bayer AG) were charged with 100 ml of an aqueous solution containing 4.9 g N-methyl morpholine (pH=10.03). Subsequent elution was effected with 200 ml 10% acetic acid. The eluate contained 4.6 g N-methyl morpholine. After this, the ion exchanger was washed with 400 ml distilled water. An additional 0.2 g N-methyl morpholine was found in the washings.
Thus, the amine was removed from the aqueous solution by 98% and readily disposed by burning. The distillate was used to prepare new elution solutions.
50 ml LEWATIT CNP 80 were charged with 500 ml waste water from cellulose processing (pH=10.31) containing 0.15% by weight N-methyl morpholine and morpholine. Elution was effected with 150 ml 10% acetic acid, whereupon washing was performed with 300 ml distilled water. Subsequently, distillation was carried out, 42.6 g condensate with an acetic acid concentration of 3.3 % being obtained from 123 g eluate (acetic acid concentration: 4.7%). The distillation residue was comprised of 5.5% acetic acid, 0.36% amine and water. By adding acetic acid to this, the elution solution for the following Example 3 was prepared, the amine having no adverse effect.
The amine was removed from the waste water by 94%.
50 ml LEWATIT CNP 80 were charged with 1000 ml waste water (pH=9.88) containing 2.86 g N-methyl morpholine. Subsequently, elution was effected with the distillation residue incurred in Example 2 and enriched with acetic acid to 10.4%. Thereby, the amine concentration fell to 1.54%. 148.2 g of this solution were required for elution. 198.2 g eluate incurred, containing 6.09% acetic acid and 2.18% amine. Thus, 72% of the amine could be eluted even without washing,.
Processing and disposal were effected as in Example 1.
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|US3475330 *||Dec 5, 1967||Oct 28, 1969||Continental Products Of Texas||Methods of removing and reclaiming ammonia ions from water|
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|AT336510B *||Title not available|
|GB1073582A *||Title not available|
|1||*||Isaeva et al., Khim. Prom st. (Moscow) 1983 (2); pp. 83 85 (English abstract).|
|2||Isaeva et al., Khim. Prom-st. (Moscow) 1983 (2); pp. 83-85 (English abstract).|
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|US5942122 *||Apr 1, 1996||Aug 24, 1999||Ngk Insulators, Ltd.||Method of deodorizing ion-exchanged purified water|
|US6113799 *||Apr 17, 1997||Sep 5, 2000||Lenzing Aktiengesellschaft||Process for selective separation of morpholine|
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|US8545704 *||May 30, 2008||Oct 1, 2013||Soonchunhyang University Industry Academy Cooperation Foundation||Method for recovering amine from amine-containing waste water|
|US8911538||Dec 22, 2011||Dec 16, 2014||Alstom Technology Ltd||Method and system for treating an effluent stream generated by a carbon capture system|
|US20090101589 *||Oct 19, 2007||Apr 23, 2009||Kiu-Seung Lee||Method for removing hydrazine compounds|
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|U.S. Classification||210/664, 203/41, 210/673, 210/677, 210/670|
|International Classification||C07C209/86, C02F1/42, C07D295/02, B01J39/04|
|Cooperative Classification||B01J39/046, C02F1/42|
|European Classification||B01J39/04D, C02F1/42|
|May 24, 1990||AS||Assignment|
Owner name: LENZING AKTIENGESELLSCHAFT, A COMPANY OF AUSTRIA,
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KORGER, DIETMAR;ASTEGGER, STEPHAN;EICHINGER, DIETER;ANDOTHERS;REEL/FRAME:005318/0268
Effective date: 19900510
|Mar 2, 1993||CC||Certificate of correction|
|Jan 23, 1995||FPAY||Fee payment|
Year of fee payment: 4
|Feb 16, 1999||FPAY||Fee payment|
Year of fee payment: 8
|Mar 12, 2003||REMI||Maintenance fee reminder mailed|
|Aug 27, 2003||LAPS||Lapse for failure to pay maintenance fees|
|Oct 21, 2003||FP||Expired due to failure to pay maintenance fee|
Effective date: 20030827